CN110565078B - Method for preparing cobalt-sulfur film on copper surface based on reverse replacement - Google Patents
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- 239000010949 copper Substances 0.000 title claims abstract description 79
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 78
- 230000002441 reversible effect Effects 0.000 title claims abstract description 53
- VRRFSFYSLSPWQY-UHFFFAOYSA-N sulfanylidenecobalt Chemical compound [Co]=S VRRFSFYSLSPWQY-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 28
- 230000008021 deposition Effects 0.000 claims abstract description 81
- 238000006073 displacement reaction Methods 0.000 claims abstract description 43
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000010408 film Substances 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 15
- 239000010409 thin film Substances 0.000 claims abstract description 13
- 239000000758 substrate Substances 0.000 claims abstract description 10
- 238000004140 cleaning Methods 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 8
- 238000005498 polishing Methods 0.000 claims abstract description 8
- 231100000719 pollutant Toxicity 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 238000006467 substitution reaction Methods 0.000 claims abstract description 7
- 239000013049 sediment Substances 0.000 claims abstract description 6
- 239000000654 additive Substances 0.000 claims abstract description 5
- 230000000996 additive effect Effects 0.000 claims abstract description 5
- 239000011248 coating agent Substances 0.000 claims abstract description 5
- 238000000576 coating method Methods 0.000 claims abstract description 5
- 150000001868 cobalt Chemical class 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract description 4
- 244000137852 Petrea volubilis Species 0.000 claims abstract description 3
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 8
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 8
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 5
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 4
- 229940044175 cobalt sulfate Drugs 0.000 claims description 4
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 4
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 238000000151 deposition Methods 0.000 description 66
- 239000000243 solution Substances 0.000 description 46
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 13
- 230000003197 catalytic effect Effects 0.000 description 10
- 229910017052 cobalt Inorganic materials 0.000 description 9
- 239000010941 cobalt Substances 0.000 description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 8
- 229910052697 platinum Inorganic materials 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000000861 blow drying Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
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Abstract
The invention relates to a method for preparing a cobalt-sulfur film on a copper surface, in particular to a method for preparing a cobalt-sulfur film on a copper surface based on reverse substitution, which comprises the following steps: s1, preparing a reverse displacement sediment liquid: the composition of the reverse displacement deposition solution and the content of each component are as follows: 10-200g/L of cobalt salt and 90-320g/L of additive, and adjusting the pH value of the deposition solution to 3-7 by using dilute sulfuric acid and the like; s2, copper sample treatment: polishing the copper substrate by using sand paper, removing oxides and pollutants on the surface, then ultrasonically cleaning in an ethanol solution, and drying by using nitrogen; s3, deposition coating: putting the copper sample into a reverse displacement deposition solution for deposition; s4, processing a cobalt-sulfur thin film copper sample: taking out the copper sample, washing the residual deposition solution with deionized water, and drying with nitrogen; the method can be used for directly preparing the high-quality cobalt-sulfur film on the copper surface, and has the advantages of simple composition of the deposition solution, less operation process, short time consumption, low cost and the like.
Description
Technical Field
The invention relates to a method for preparing a cobalt-sulfur film on a copper surface, in particular to a method for preparing a cobalt-sulfur film on a copper surface based on reverse substitution.
Background
The electrolytic reaction of water consists of two half-reactions, the reduction reaction of water, respectively, being called Hydrogen Evolution Reaction (HER) and the oxidation reaction of water, being called Oxygen Evolution Reaction (OER). Under the standard state, the voltage of the reversible electrolytic cell for the water decomposition reaction is 1.23V, but the dynamic obstruction exists in the hydrogen evolution reaction and the oxygen evolution reaction processes, so that the applied voltage required by the practical electrolytic cell is far more than 1.23V. It has been found that the use of noble metal catalytic materials, such as platinum-based catalytic materials, on the electrode surface effectively reduces the overpotential required for the overall water splitting reaction. But their large-scale use is severely hampered by the scarcity and high price of precious metal materials. Therefore, it is of great significance to find suitable non-noble metal catalytic materials to replace noble metal catalytic materials so as to reduce the cost of developing efficient electrolytic water catalytic materials.
The cobalt-sulfur film has excellent electrolytic water catalytic performance, and can be used as a non-noble metal catalytic material for catalyzing electrolytic water decomposition reaction. In recent years, a great deal of research has been focused on a simple method for preparing cobalt-sulfur thin films. Copper is a common electrode material, and a common method for preparing a cobalt-sulfur thin film on the surface of copper is to prepare a pure cobalt thin film on the surface of copper by electroplating or vapor deposition and the like, and then to vulcanize the thin film by using a sulfur-containing atmosphere or a sulfide salt solution to prepare the cobalt-sulfur thin film.
The displacement deposition method has the advantages of simple process, high deposition speed, low cost and the like. However, the standard electrode potential of copper (ECu2+/Cu ═ 0.337V) is significantly higher than that of nickel (ECo2+/Co ═ -0.277V), and thus it is difficult to prepare a cobalt-sulfur thin film on the copper surface by displacement deposition.
Disclosure of Invention
The invention provides a method for preparing a cobalt-sulfur film on a copper surface based on reverse replacement, which solves the technical problem of overcoming the defects of complex process and the like of the existing method for preparing the cobalt-sulfur film on the copper surface and aims to reduce the process complexity and the comprehensive cost for preparing the cobalt-sulfur film on the copper surface.
The technical scheme adopted by the invention is as follows:
a method for preparing a cobalt-sulfur film on a copper surface based on reverse substitution is characterized by comprising the following steps:
s1, preparing a reverse displacement sediment liquid: the composition of the reverse displacement deposition solution and the content of each component are as follows: 10-200g/L of cobalt salt and 90-320g/L of additive, and adjusting the pH value of the deposition solution to 3-7 by using dilute sulfuric acid and the like;
s2, copper sample treatment: polishing the copper substrate by using sand paper, removing oxides and pollutants on the surface, then ultrasonically cleaning in an ethanol solution, and drying by using nitrogen;
s3, deposition coating: putting the copper sample into a reverse displacement deposition solution for deposition;
s4, processing a cobalt-sulfur thin film copper sample: and taking out the copper sample, washing the residual deposition solution with deionized water, and drying with nitrogen.
In the step S1, the cobalt salt is one or more of cobalt sulfate, cobalt chloride, and cobalt nitrate.
In the step S1, the additive is one of thiosulfuric acid and thiourea.
In the step S2, 400#, 800#, 1200# sandpaper is used to polish the copper substrate.
In the step S3, the deposition coating conditions are as follows: the temperature of the reverse displacement deposition solution is 20-80 ℃, and the deposition time is 5-60 minutes.
The invention has the beneficial effects that: the method can be used for directly preparing the high-quality cobalt-sulfur film on the copper surface, and has the advantages of simple composition of the deposition solution, less operation process, short time consumption, low cost and the like. The prepared cobalt-sulfur film has excellent electro-catalytic water decomposition performance, and reaches 10mA/cm in 1 mol per liter of potassium hydroxide solution2The required voltage at the oxygen evolution current density of (1.674V) (1.774V is required for the platinum sheet under the same conditions); reaching 40mA/cm2The required voltage for hydrogen evolution current density of (2) was 0.232V (under the same conditions, the required voltage for platinum sheet was 0.237V).
Drawings
FIG. 1 is a graph of the stable potentials of cobalt and copper in a reverse displacement deposition solution;
FIG. 2 shows the X-ray diffraction analysis results of the prepared cobalt-sulfur thin film;
FIG. 3 is a polarization curve of oxygen evolution reaction of a cobalt-sulfur thin film on copper, platinum and copper surfaces in 1 mol/L KOH solution;
FIG. 4 is a graph showing the polarization curves of hydrogen evolution reactions of cobalt-sulfur thin films on copper, platinum and copper surfaces in 1 mol/L KOH solution.
Detailed Description
The technical scheme of the invention is further explained by specific embodiments in the following with the accompanying drawings:
example 1
The invention designs a method for preparing a cobalt-sulfur film on a copper surface based on reverse displacement, wherein the reverse displacement deposition solution comprises the following components in percentage by weight: cobalt chloride 20g/L, sodium thiosulfate 120g/L, dilute sulfuric acid, etc. to adjust the pH value of the deposition solution to 5. Polishing the copper substrate by using 400#, 800# and 1200# sandpaper respectively to remove oxides and pollutants on the surface; then ultrasonically cleaning in an ethanol solution, and drying by nitrogen; then putting the polished and cleaned copper sample into a reverse displacement deposition solution for deposition, wherein the deposition conditions are as follows: the temperature of the reverse displacement deposition solution is 20 ℃, and the deposition time is 10 minutes; and after the deposition is finished, taking out the copper sheet, washing the residual deposition solution with deionized water, and blow-drying with nitrogen to obtain the cobalt-sulfur film on the copper surface.
Because sodium thiosulfate exists in the reverse displacement deposition solution, the electrode potential of copper in the reverse displacement deposition solution is greatly shifted negatively and is lower than the electrode potential of cobalt in the reverse displacement deposition solution, so that the cobalt is reversely displaced and deposited on the surface of copper. In addition, because the reverse displacement sediment liquid is in an acidic environment, the sodium thiosulfate can decompose sulfur under the acidic condition. During deposition, the two processes exist simultaneously, so that cobalt generated by reverse displacement deposition and sulfur generated by decomposition of sodium thiosulfate can be combined into cobalt-sulfur compounds, and finally, a cobalt-sulfur thin film consisting of pure cobalt and the cobalt-sulfur compounds is formed. The analysis shows that the cobalt-sulfur compound is Co3S2。
The cobalt-sulfur film can be obtained on the surface of the industrial pure copper sheet by adopting the method for preparing the cobalt-sulfur film on the surface of the copper based on reverse replacement. The stable potentials of copper and cobalt in the reverse displacement deposition solution were-0.44V and-0.38V, respectively, as shown in fig. 1. The stable potential of copper in the reverse displacement deposition solution is lower than that of cobalt in the reverse displacement deposition solution, so that the reverse displacement deposition of cobalt on the copper surface is possible. The diffraction pattern of the cobalt-sulfur film on the copper surface was measured by XRD diffractometer, and the analysis result is shown in FIG. 2, which indicates that the cobalt-sulfur film deposited by reverse substitution on the copper surface consists of Co and Co3S2And (4) forming. The catalytic electrolysis water decomposition effect of pure copper, pure platinum and a cobalt-sulfur film on the surface of copper in 1 mol/L potassium hydroxide solution is respectively tested, and an oxygen evolution reaction polarization curve and a hydrogen evolution reaction polarization curve are respectively shown in fig. 3 and fig. 4. The cobalt-sulfur film can be found to have catalytic electrolysis water oxygen evolution reaction performance superior to that of platinum and catalytic electrolysis water hydrogen evolution reaction performance close to that of platinum.
Example 2
The invention designs a method for preparing a cobalt-sulfur film on a copper surface based on reverse displacement, wherein the reverse displacement deposition solution comprises the following components in percentage by weight: cobalt sulfate 200g/L, sodium thiosulfate 90g/L, dilute sulfuric acid, etc. to adjust the pH value of the deposition solution to 7. Polishing the copper substrate by using 400#, 800# and 1200# sandpaper respectively to remove oxides and pollutants on the surface; then ultrasonically cleaning in an ethanol solution, and drying by nitrogen; then putting the polished and cleaned copper sample into a reverse displacement deposition solution for deposition, wherein the deposition conditions are as follows: the temperature of the reverse displacement deposition solution is 40 ℃, and the deposition time is 20 minutes; and after the deposition is finished, taking out the copper sheet, washing the residual deposition solution by using deionized water, and drying by using nitrogen to obtain the cobalt-sulfur film on the surface of the copper.
Example 3
The invention designs a method for preparing a cobalt-sulfur film on a copper surface based on reverse displacement, wherein the reverse displacement deposition solution comprises the following components in percentage by weight: cobalt nitrate 10g/L, sodium thiosulfate 320g/L, dilute sulfuric acid, etc. to adjust the pH value of the deposition solution to 3. Polishing the copper substrate by using 400#, 800# and 1200# sandpaper respectively to remove oxides and pollutants on the surface; then ultrasonically cleaning in an ethanol solution, and drying by nitrogen; then putting the polished and cleaned copper sample into a reverse displacement deposition solution for deposition, wherein the deposition conditions are as follows: the temperature of the reverse displacement deposition solution is 80 ℃, and the deposition time is 5 minutes; and after the deposition is finished, taking out the copper sheet, washing the residual deposition solution by using deionized water, and drying by using nitrogen to obtain the cobalt-sulfur film on the surface of the copper.
Example 4
The invention designs a method for preparing a cobalt-sulfur film on a copper surface based on reverse displacement, wherein the reverse displacement deposition solution comprises the following components in percentage by weight: 30g/L of cobalt chloride, 40g/L of cobalt nitrate and 240g/L of thiourea, and the pH value of the sediment solution is adjusted to 6 by using dilute sulfuric acid and the like. Polishing the copper substrate by using 400#, 800# and 1200# sandpaper respectively to remove oxides and pollutants on the surface; then ultrasonically cleaning in an ethanol solution, and drying by nitrogen; then putting the polished and cleaned copper sample into a reverse displacement deposition solution for deposition, wherein the deposition conditions are as follows: the temperature of the reverse displacement deposition solution is 60 ℃, and the deposition time is 60 minutes; and after the deposition is finished, taking out the copper sheet, washing the residual deposition solution by using deionized water, and drying by using nitrogen to obtain the cobalt-sulfur film on the surface of the copper.
Example 5
The invention designs a method for preparing a cobalt-sulfur film on a copper surface based on reverse displacement, wherein the reverse displacement deposition solution comprises the following components in percentage by weight: 40g/L of cobalt nitrate, 40g/L of cobalt sulfate and 180g/L of sodium thiosulfate, and the pH value of the sediment solution is adjusted to 6 by using dilute sulfuric acid and the like. Polishing the copper substrate by using 400#, 800# and 1200# sandpaper respectively to remove oxides and pollutants on the surface; then ultrasonically cleaning in an ethanol solution, and drying by nitrogen; then putting the polished and cleaned copper sample into a reverse displacement deposition solution for deposition, wherein the deposition conditions are as follows: the temperature of the reverse displacement deposition solution is 50 ℃, and the deposition time is 40 minutes; and after the deposition is finished, taking out the copper sheet, washing the residual deposition solution by using deionized water, and drying by using nitrogen to obtain the cobalt-sulfur film on the surface of the copper.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (3)
1. A method for preparing a cobalt-sulfur film on a copper surface based on reverse substitution is characterized by comprising the following steps:
s1, preparing a reverse displacement sediment liquid: the composition of the reverse displacement deposition solution and the content of each component are as follows: 10-200g/L of cobalt salt and 90-320g/L of additive, wherein the additive is one of sodium thiosulfate and thiourea, and the pH value of the deposition solution is adjusted to 3-7 by using dilute sulfuric acid;
s2, copper sample treatment: polishing the copper substrate by using sand paper, removing oxides and pollutants on the surface, then ultrasonically cleaning in an ethanol solution, and drying by using nitrogen;
s3, deposition coating: putting a copper sample into the reverse displacement deposition solution for deposition, wherein the deposition coating conditions are as follows: the temperature of the reverse displacement deposition solution is 20-80 ℃, and the deposition time is 5-60 minutes;
s4, processing a cobalt-sulfur thin film copper sample: and taking out the copper sample, washing the residual deposition solution with deionized water, and drying with nitrogen.
2. The method for preparing the cobalt-sulfur film on the copper surface based on the reverse substitution as claimed in claim 1, wherein: in the step S1, the cobalt salt is one or more of cobalt sulfate, cobalt chloride, and cobalt nitrate.
3. The method for preparing the cobalt-sulfur film on the copper surface based on the reverse substitution as claimed in claim 1, wherein: in the step S2, 400#, 800#, 1200# sandpaper is used to polish the copper substrate.
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| US7407689B2 (en) * | 2003-06-26 | 2008-08-05 | Atotech Deutschland Gmbh | Aqueous acidic immersion plating solutions and methods for plating on aluminum and aluminum alloys |
| CN102181847A (en) * | 2011-04-14 | 2011-09-14 | 山东大学 | Method for depositing Cu-Zn-Tin-Sulfur film by ethanol heat |
| CN103094524B (en) * | 2012-12-31 | 2015-10-07 | 浙江工业大学 | A kind of tin alloy membrane electrode and application thereof |
| CN104213107A (en) * | 2014-09-19 | 2014-12-17 | 广西师范大学 | Zinc dipping solution for aluminum or aluminum alloy and preparing method and zinc dipping technology therefore |
| CN104561961A (en) * | 2014-12-27 | 2015-04-29 | 广东致卓精密金属科技有限公司 | Chemical cobalt-nickel plating alloy liquid and process |
| CN109518169A (en) * | 2018-11-26 | 2019-03-26 | 新疆大学 | A kind of preparation method and application of sulphur cobalt nickel nano film cladding titanium dioxide nano band |
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